1-Bromo-3-methylbutane → 4-(3-Methylbutoxy)-2-nitroaniline

HRID 537292Notes

Reaction equation

HRID 537292 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([OH:8])=[CH:4][C:3]=1[N+:9]([O-:11])=[O:10].Br[CH2:13][CH2:14][CH:15]([CH3:17])[CH3:16].O[Li].O>CCO>[CH3:16][CH:15]([CH3:17])[CH2:14][CH2:13][O:8][C:5]1[CH:6]=[CH:7][C:2]([NH2:1])=[C:3]([N+:9]([O-:11])=[O:10])[CH:4]=1

Participants

5

Reactant 3

HCID 78911-Bromo-3-methylbutane2×HCID 168937Lithium hydroxide, monohydrate2×HCID 37588824-Amino-3-Nitrophenol

Product 1

HCID 2932934-(3-Methylbutoxy)-2-nitroanilineYield 91%

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Procedure

A 500 mL 3-neck flask fitted with a stir-bar, condenser, and an Ar inlet was charged with 4-amino-3-nitrophenol (12.0 g, 77.9 mmol), 1-bromo-3-methylbutane (14.7 g, 97.3 mmol), LiOH.H2O (6.55 g, 156 mmol), and EtOH (120 mL). The resultant solution was heated at reflux overnight. Another 3 mL of 1-bromo-3-methylbutane and 1 g of LiOH.H2O were added, and the mixture was heated at reflux overnight again. The solution was cooled and partitioned with EtOAc (250 mL) and H2O (200 mL). The organic phase was washed with 1% aqueous LiOH (2×200 mL), H2O (200 mL), and brine (200 mL), filtered through phase separation paper, and concentrated to a dark red solid. The material was dried to give 15.9 g of 46b as a red solid (91%). 1H NMR (60 MHz, CDCl3): δ 7.2 (d, 1H), 7.0 (dd, 1H), 6.7 (d, 1H), 6.0 (bs, 2H), 3.9 (t, 2H), 1.8-1.4 (m, 3H), 1.0 (d, 6H) ppm. HPLC analysis (15:10:75 H2O:A1:MeOH) showed a purity of 94% with a retention time of 8.6 min.

Workup

  1. customA 500 mL 3-neck flask fitted with a stir-bar, condenser
  2. temperatureat reflux overnight
  3. temperaturethe mixture was heated
  4. temperatureat reflux overnight again
  5. temperatureThe solution was cooled
  6. custompartitioned with EtOAc (250 mL) and H2O (200 mL)
  7. washThe organic phase was washed with 1% aqueous LiOH (2×200 mL), H2O (200 mL), and brine (200 mL)
  8. filtrationfiltered through phase separation paper
  9. concentrationconcentrated to a dark red solid
  10. customThe material was dried

Sources & evidence

ORD record
ord-7c663cb1a79445999109ab31fd1c2dda
Source dataset
uspto-grants-2014_10
Patent number
US08859780B2

Reaction notes

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